US4303628A - Crystalline zeolite powder of type A (IV) - Google Patents

Crystalline zeolite powder of type A (IV) Download PDF

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Publication number
US4303628A
US4303628A US05/846,014 US84601477A US4303628A US 4303628 A US4303628 A US 4303628A US 84601477 A US84601477 A US 84601477A US 4303628 A US4303628 A US 4303628A
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United States
Prior art keywords
grams
sub
sio
added
aqueous sodium
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US05/846,014
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English (en)
Inventor
Hans Strack
Wolfgang Roebke
Dieter Kneitel
Ehrfried Parr
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Evonik Operations GmbH
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Evonik Degussa GmbH
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Assigned to DEGUSSA AKTIENGESELLSCHAFT, A CORP. OF GERMANY reassignment DEGUSSA AKTIENGESELLSCHAFT, A CORP. OF GERMANY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • C01B33/28—Base exchange silicates, e.g. zeolites
    • C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
    • C01B33/2815—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures of type A (UNION CARBIDE trade name; corresponds to GRACE's types Z-12 or Z-12L)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S423/00—Chemistry of inorganic compounds
    • Y10S423/24—LTA, e.g. A, alpha, ZK-4, ZK-21, ZK-22

Definitions

  • the invention is directed to a crystalline zeolite powder of Type A having the composition
  • M is a metal cation, e.g., sodium, potassium, lithium, calcium, magnesium or barium, n its valence and y has a value up to 6 with 50 weight % of the particles not over 4.9 ⁇ and a process for the production of the crystalline zeolite powder by means of a hydrothermal crystallization of an alkali aluminate silicate mixture, as well as its use in washing, rinsing and cleansing agents.
  • M is a metal cation, e.g., sodium, potassium, lithium, calcium, magnesium or barium
  • Zeolite molecular sieves and their special properties for ion exchange and adsorption have been known for a long time. Their synthesis depends on heating an aqueous synthesis mixture with the components a Na 2 O ⁇ b Al 2 O 3 ⁇ c SiO 2 to a temperature between 50° and 300° C. According to the composition of the starting mixture, reaction temperature and reaction time there are obtained different structured compounds of the general formula
  • Sodium can be replaced by other mono- and divalent metal cations, e.g., potassium, lithium, cesium, magnesium, barium and strontium.
  • the molecular sieves are converted into molded articles with a suitable binder.
  • the production of the molded article means a great industrial expense with simultaneous reduction of the effect because of the binder component.
  • the reaction speed is greatly retarded, which, e.g., makes cumbersome the drying of organic liquids. It is, therefore, significant to add molecular sieve powders in many uses.
  • the invention is based on the problem of creating a process of synthesizing and providing a powdery zeolitic molecular sieve of Type A having a smaller particle size without formation of grit components (particles >45 ⁇ ), which molecular sieve is especially useful as an ion exchange, e.g., for water softening.
  • the absence of grit as well as a smaller particle size is indispensable for a number of uses within the invention, e.g., use of such molecular sieves, e.g., as phosphate replacements in washing, rinsing and cleansing, processes.
  • washing, rinsing and cleansing processes especially in machines, imply indeed a lasting suspension of the molecular sieve (as a result of a slight tendency for quiescent setting) in the liquor in order to make possible a residue free rinsing after completion of the process.
  • the purpose of the invention is to produce a crystalline zeolite powder of Type A with the composition
  • M is a metal cation, e.g., a Group Ia metal (alkali metal) such as sodium, potassium, lithium or cesium or a Group IIa metal (alkaline earth metal) such as magnesium, calcium, strontium or barium, n is its valence and y has a value up to 6 with 50 weight % of the particles having a maximum particle size of 4.9 ⁇ and with a particle spectrum:
  • a metal cation e.g., a Group Ia metal (alkali metal) such as sodium, potassium, lithium or cesium or a Group IIa metal (alkaline earth metal) such as magnesium, calcium, strontium or barium
  • n is its valence and y has a value up to 6 with 50 weight % of the particles having a maximum particle size of 4.9 ⁇ and with a particle spectrum:
  • a further object of the invention is the development of a process for the production of the crystalline zeolite powder of the invention by hydrothermally crystallizing a SiO 2 , Al 2 O 3 , Na 2 O and water containing alkali aluminate, water, silicate synthesis mixture with an optional tempering step wherein in a given case during the crystallization or tempering step instead of stirring shearing forces are employed.
  • the process comprises mixing with stirring (1) an aqueous alkali silicate solution and (2) aqueous sodium hydroxide with a NaOH content of 0.1 to 500 grams/l and/or (3) aqueous sodium aluminate liquor which contains 0.1 to 100 grams/l of Al 2 O 3 and 1 to 200 grams/l of Na 2 O, one of components (1) and (2) or (3) being present in a container and the other being added thereto while preventing for a time of 10 to 30 minutes the formation of an insoluble gel having an SiO 2 /Al 2 O 3 ratio of from 2 to 50:1, adding with stirring an aqueous sodium aluminate which contains 10 to 200 grams/l of Al 2 O 3 and 10 to 250 grams/l of Na 2 O and having a temperature of 10° to 100° C. and allowing the thus obtained synthesis mixture to crystallize at a temperature within between 20° and 175° C. inside at least 15 minutes.
  • the alkali silicate solution has 50 to 150 grams of Na 2 O/l and 200 to 450 grams of SiO 2 /l.
  • Shearing can be accomplished, for example, with an energy introduction of 0,4 to 2 KW/m 3 .
  • the aqueous sodium aluminate having a content of 10 to 200 grams of Al 2 O 3 /l and 10 to 250 grams of Na 2 O/l can be added stepwise to the reaction mixture, e.g., in two steps, wherein the speed of addition in the second step is 2 to 10 times higher than in the first step.
  • stirrers there can be used in the process of the invention shearing forces, for which purpose known apparatuses can be employed. These known procedures increase the particle fineness, but are not necessary for carrying out the process of the invention.
  • the synthesis mixture arising by the addition of a higher concentrated alkali aluminate liquor can contain the individual components in the molar ratios which are used in the known processes.
  • Such known processes are described in Milton German Pat. No. 1,038,017, Milton U.S. Pat. No. 2,882,243 and Weber German Auslegeschrift No. 1,095,795.
  • the Weber Auslegeschrift shows molar ratios of Na 2 O: Al 2 O 3 of from 2 to 4:1.
  • shearing as is used in the present case, are all mechanical stresses causing comminution of discrete particles found in the suspension, which rest predominantly on true shearing action.
  • the shearing can be carried out discontinuously or continuously.
  • a turbine stirrer for example, the EKATO turbine stirrer.
  • crown gear dissolvers dispersing pumps, centrifugal pumps and other apparatus for the shearing.
  • the crystallization in the present case can be carried out at 93° C.
  • crystallization is preferably carried out at 93° C., this temperature can be varied, e.g., between 90° and 100° C.
  • the tempering time begins at the point at which the crystallization is finished. This is recognizable by the development of maximum ion exchange power, the reaching of maximum X-ray line intensity and the production of about 22.5% water vapor absorption. In practice a foundation is laid based on empirical values determined by optimization of a recipe.
  • a shearing influence up to the end of the crystallization phase can be so intensified that the average particle diameter can be reduced to a very low value. Thereby the value for the limiting particle and its percentage in the product likewise is reduced. However, shearing carried out during the temperature step has exclusive influence on the limiting particle and its portion of all of the particles.
  • the invention concerns the use of the zeolitic molecular sieves of Type A, obtainable by the process of the invention, as ion exchangers, e.g., for water softening, particularly as phosphate substitutes in washing, rinsing and cleansing agents.
  • washing agents are combinations of surface active washing materials, but for the most part also contain other, predominantly inorganic additives which contribute to the washing result or are necessary for the process of production and the outer product quality.
  • the composition of the washing agent is varied. It depends on the type of fiber, dyeing and washing temperature, as well as apart therefrom whether the washing is by hand, e.g., in a kettle, in a home washing machine, or in a laundry. Most washing agents are pourable powders. However, there are also liquid and pasty products (see Ullmann's Enzyklopadie der ischen Chemie, 3rd edition, Vol. 18, Urban & Schwarzenberg, Kunststoff, 1967).
  • the crystalline zeolite powder of Type A produced by the invention has the advantage that it is already produced in grit-free form and contains smaller particles. Therefore, when it is used as a phosphate substitute in washing and cleansing agents, it can be easily held in suspension in the liquor employed, as well as particularly easily rinsed from washing and cleansing machines and their loads.
  • alkali aluminum silicates of the invention has the advantage that the loading of the environment with phosphate will no longer occur. Eutrophication of the waters, seas and rivers will no longer result to the presently known extent if the molecular sieves of the invention are employed in the washing agent.
  • the washing agents are the same as those conventionally employed in the art.
  • the conventional surfactants or detergents e.g., anionic, cationic and nonionic detergents.
  • detergents there can be used, for example, higher alkyl sulfate detergents, particularly the alkali metal salts of such sulfates, those having 8 to 22 carbon atoms in the alkyl residue such as sodium lauryl sulfate, potassium lauryl sulfate, sodium octadecyl sulfate, sodium coconut fatty alcohol sulfate, sodium octanyl sulfate, sodium alkyl (C 14 -C 18 ) sulfate, as well as the corresponding long chain aliphatic sulfonates, e.g., sodium octanyl sulfonate, sodium dodecyl sulfonate, sodium tetradecyl sulfonate, sodium octadecyl sulfonate, potassium dodecyl sulfonate, ammonium dodecyl sulfonate, sodium decyl
  • bleaching agents e.g., sodium perborate
  • water softeners e.g., borax
  • other additives including sodium carbonate, sodium sulfate and potassium carbonate, as well as polyvinyl alcohol, carboxymethyl cellulose, etc.
  • the other materials can be omitted if desired.
  • compositions can comprise, consist essentially of, or consist of the materials set forth.
  • POC is a poly(hydroxycarboxylic) prepared by the Cannizzaro reaction of a poly(aldehydocarboxylate), see Haschke U.S. Pat. No. 3,923,742.
  • the particle size determination was carried out by Coulter Counter measurement.
  • the particle size determination was carried out by Coulter Counter measurement.
  • the particle size determination was carried out by Coulter Counter measurement.
  • the sodium aluminate liquor contained 161 grams/l Na 2 O and 105 grams/l Al 2 O 3 .
  • the synthesis mixture obtained was warmed to 85° C. and crystallized for three hours.
  • the crystalline product was X-ray graphically pure zeolite A having the following particle spectrum:
  • the particle size determination was carried out by Coulter Counter measurement.
  • Sodium aluminum silicate according to any one of Examples 1 to 3 45.0 weight % (dried for 6 hours at 90° C., water content 16.8 weight %).
  • Washing agent powder 35.0 weight %.
  • the washing agent powder was produced, for example, by hot drying the following compositions:
  • the washing agent was produced by mixing the three constituents in powder form.
  • Sodium aluminum silicate prepared according to any one of Examples 1 to 3 (dried for 6 hours at 90° C., water content 16.8 weight %): 40.0 weight %.
  • Soda sodium carbonate: 15.0 weight %.
  • Sodium citrate 5.0 weight %.
  • Carboxymethyl cellulose 1.5 weight %.
  • Optical brightener 0.2 weight %.
  • the washing agent was produced by spraying the ethoxylation product (nonionic surfactant) on the powder particles consisting of the remaining constituents.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Detergent Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
US05/846,014 1976-11-11 1977-10-27 Crystalline zeolite powder of type A (IV) Expired - Lifetime US4303628A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2651419 1976-11-11
DE19762651419 DE2651419A1 (de) 1976-11-11 1976-11-11 Kristallines zeolithpulver des typs a iv

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US06260764 Division 1981-05-05

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US06/474,895 Expired - Lifetime US4551322A (en) 1976-11-11 1983-03-14 Process for preparing zeolite powder of type A (IV)

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US (2) US4303628A (enrdf_load_stackoverflow)
JP (3) JPS5361596A (enrdf_load_stackoverflow)
BE (1) BE860757A (enrdf_load_stackoverflow)
BR (1) BR7707167A (enrdf_load_stackoverflow)
CA (1) CA1082163A (enrdf_load_stackoverflow)
CH (1) CH631947A5 (enrdf_load_stackoverflow)
DE (1) DE2651419A1 (enrdf_load_stackoverflow)
ES (1) ES463996A1 (enrdf_load_stackoverflow)
FR (1) FR2370689A1 (enrdf_load_stackoverflow)
GB (1) GB1571536A (enrdf_load_stackoverflow)
IT (1) IT1202414B (enrdf_load_stackoverflow)
NL (1) NL7709210A (enrdf_load_stackoverflow)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4339419A (en) * 1980-02-25 1982-07-13 Degussa Ag Process for the production of crystalline zeolite powder of type A
US4339418A (en) * 1980-02-26 1982-07-13 Degussa Ag Process for the production of zeolite A
US4339417A (en) * 1980-02-26 1982-07-13 Degussa Ag Process for the production of crystalline zeolite A
US4339420A (en) * 1980-02-26 1982-07-13 Degussa Ag Process for the production of zeolite A
US4435216A (en) 1981-08-20 1984-03-06 Degussa Aktiengesellschaft Process for the accelerated solidification of hydraulic cement mixture
US4454056A (en) * 1982-03-10 1984-06-12 Degussa Aktiengesellschaft Process for the production of zeolites modified on the surface with organosilanes
US4542115A (en) * 1981-08-17 1985-09-17 Degussa Aktiengesellschaft Zeolite granulate, process for its production
US4551322A (en) * 1976-11-11 1985-11-05 Degussa Aktiengesellschaft Process for preparing zeolite powder of type A (IV)
US4671887A (en) * 1984-12-05 1987-06-09 Degussa Aktiengesellschaft Aqueous stable suspensions of water insoluble silicates capable of binding calcium ions and their use for the production of washing and cleaning agents
US5474753A (en) * 1990-11-09 1995-12-12 Laviosa Rhone-Poulenc Preparation of crystalline 4A zeolites
US5645811A (en) * 1993-03-25 1997-07-08 Henkel Kommanditgesellschaft Auf Aktien Process for the production of very fine-particle zeolitic alkali metal aluminum silicates
US20060200917A1 (en) * 2005-02-11 2006-09-14 The Board Of Regents Of The University Of Texas System Color compositions and methods of manufacture
US20070033747A1 (en) * 2005-06-17 2007-02-15 The Board Of Regents Of The University Of Texas System Organic/Inorganic Lewis Acid Composite Materials
US20070277702A1 (en) * 2002-06-19 2007-12-06 Russell Chianelli Color compositions

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1165442B (it) * 1979-01-26 1987-04-22 Montedison Spa Zeoliti di tipo a,ad elevato grado di cristallinita' e a granulometria fine e processo per la loro produzione
DE2910147A1 (de) * 1979-03-15 1980-10-30 Degussa Verfahren zur herstellung von amorphen natriumaluminiumsilikaten
DE3516660A1 (de) 1985-05-09 1986-11-13 Degussa Ag, 6000 Frankfurt Pulverfoermiges bindemittelkonzentrat
EP0356625A1 (de) * 1988-08-12 1990-03-07 Degussa Aktiengesellschaft Zeolithpulver des Typs Na A für die Verwendung in Flüssigwaschmitteln
EP0357989B1 (de) * 1988-08-12 1995-02-08 Degussa Aktiengesellschaft Zeolithpulver des Typs NaA für die Verwendung in Flüssigwaschmitteln

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US2882243A (en) * 1953-12-24 1959-04-14 Union Carbide Corp Molecular sieve adsorbents
US3058805A (en) * 1958-10-03 1962-10-16 Bayer Ag Process for the production of sodium zeolite a
DE2412837A1 (de) * 1973-04-13 1974-10-31 Henkel & Cie Gmbh Verfahren zum waschen und reinigen der oberflaechen von festen werkstoffen, insbesondere von textilien, sowie mittel zur durchfuehrung des verfahrens
US3985669A (en) * 1974-06-17 1976-10-12 The Procter & Gamble Company Detergent compositions
US4041135A (en) * 1975-07-25 1977-08-09 J. M. Huber Corporation Production of high capacity inorganic crystalline base exchange materials
US4073867A (en) * 1975-04-18 1978-02-14 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Process for the production of crystalline zeolitic molecular sieves of type A

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US3310373A (en) 1963-04-03 1967-03-21 Mobil Oil Corp Method for producing crystalline aluminosilicates
NO148854C (no) * 1973-04-13 1985-05-29 Henkel Kgaa Pulverformet til kornet vaske- eller blekemiddelblanding, uten eller med redusert fosfatinnhold
AR208392A1 (es) * 1973-05-07 1976-12-27 Henkel & Cie Gmbh Composicion para lavar blanquear o limpiar materiales resistentes especialmente textiles adicional a la patente no 201687 adicional a la no 253286
US4605509A (en) * 1973-05-11 1986-08-12 The Procter & Gamble Company Detergent compositions containing sodium aluminosilicate builders
CA1037815A (en) * 1973-06-20 1978-09-05 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Process for the production of solid, pourable washing or cleaning agents with a content of a calcium binding silicate
DE2433485A1 (de) * 1973-07-16 1975-02-06 Procter & Gamble Zur verwendung in waschmitteln geeignete aluminosilikat-ionenaustauscher
US4274975A (en) * 1974-03-11 1981-06-23 The Procter & Gamble Company Detergent composition
DE2447021C3 (de) 1974-10-02 1984-03-22 Degussa Ag, 6000 Frankfurt Kristallines Zeolithpulver des Typs A und das Verfahren zu seiner Herstellung
US4066394A (en) * 1974-12-30 1978-01-03 Colgate-Palmolive Reusable zeolite water softener for clothes washing
DE2514399C2 (de) * 1975-04-02 1987-01-29 Degussa Ag, 6000 Frankfurt Verfahren zur Herstellung von Aluminiumsilikaten
DE2651420A1 (de) * 1976-11-11 1978-05-18 Degussa Kristallines zeolithpulver des typs a v
DE2651485A1 (de) * 1976-11-11 1978-05-24 Degussa Kristallines zeolithpulver des typs a i
DE2651437A1 (de) * 1976-11-11 1978-05-18 Degussa Kristallines zeolithpulver des typs a vi
DE2651419A1 (de) * 1976-11-11 1978-05-18 Degussa Kristallines zeolithpulver des typs a iv
DE2651436A1 (de) * 1976-11-11 1978-05-18 Degussa Kristallines zeolithpulver des typs a iii

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2882243A (en) * 1953-12-24 1959-04-14 Union Carbide Corp Molecular sieve adsorbents
US3058805A (en) * 1958-10-03 1962-10-16 Bayer Ag Process for the production of sodium zeolite a
DE2412837A1 (de) * 1973-04-13 1974-10-31 Henkel & Cie Gmbh Verfahren zum waschen und reinigen der oberflaechen von festen werkstoffen, insbesondere von textilien, sowie mittel zur durchfuehrung des verfahrens
US3985669A (en) * 1974-06-17 1976-10-12 The Procter & Gamble Company Detergent compositions
US4073867A (en) * 1975-04-18 1978-02-14 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Process for the production of crystalline zeolitic molecular sieves of type A
US4041135A (en) * 1975-07-25 1977-08-09 J. M. Huber Corporation Production of high capacity inorganic crystalline base exchange materials

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4551322A (en) * 1976-11-11 1985-11-05 Degussa Aktiengesellschaft Process for preparing zeolite powder of type A (IV)
US4339419A (en) * 1980-02-25 1982-07-13 Degussa Ag Process for the production of crystalline zeolite powder of type A
US4339418A (en) * 1980-02-26 1982-07-13 Degussa Ag Process for the production of zeolite A
US4339417A (en) * 1980-02-26 1982-07-13 Degussa Ag Process for the production of crystalline zeolite A
US4339420A (en) * 1980-02-26 1982-07-13 Degussa Ag Process for the production of zeolite A
US4542115A (en) * 1981-08-17 1985-09-17 Degussa Aktiengesellschaft Zeolite granulate, process for its production
US4435216A (en) 1981-08-20 1984-03-06 Degussa Aktiengesellschaft Process for the accelerated solidification of hydraulic cement mixture
US4454056A (en) * 1982-03-10 1984-06-12 Degussa Aktiengesellschaft Process for the production of zeolites modified on the surface with organosilanes
US4671887A (en) * 1984-12-05 1987-06-09 Degussa Aktiengesellschaft Aqueous stable suspensions of water insoluble silicates capable of binding calcium ions and their use for the production of washing and cleaning agents
US5474753A (en) * 1990-11-09 1995-12-12 Laviosa Rhone-Poulenc Preparation of crystalline 4A zeolites
US5645811A (en) * 1993-03-25 1997-07-08 Henkel Kommanditgesellschaft Auf Aktien Process for the production of very fine-particle zeolitic alkali metal aluminum silicates
US20070277702A1 (en) * 2002-06-19 2007-12-06 Russell Chianelli Color compositions
US7429294B2 (en) 2002-06-19 2008-09-30 Board Of Regents, The University Of Texas System Color compositions
US20060200917A1 (en) * 2005-02-11 2006-09-14 The Board Of Regents Of The University Of Texas System Color compositions and methods of manufacture
US7425235B2 (en) 2005-02-11 2008-09-16 The Board Of Regents Of The University Of Texas System Color compositions and methods of manufacture
US20070033747A1 (en) * 2005-06-17 2007-02-15 The Board Of Regents Of The University Of Texas System Organic/Inorganic Lewis Acid Composite Materials

Also Published As

Publication number Publication date
IT1202414B (it) 1989-02-09
CH631947A5 (de) 1982-09-15
JPS6324928B2 (enrdf_load_stackoverflow) 1988-05-23
NL7709210A (nl) 1978-05-16
CA1082163A (en) 1980-07-22
FR2370689B1 (enrdf_load_stackoverflow) 1980-06-06
BE860757A (fr) 1978-05-10
ES463996A1 (es) 1978-07-16
JPS5727918A (en) 1982-02-15
BR7707167A (pt) 1978-08-01
GB1571536A (en) 1980-07-16
JPS5723697A (en) 1982-02-06
DE2651419A1 (de) 1978-05-18
US4551322A (en) 1985-11-05
FR2370689A1 (fr) 1978-06-09
JPS5361596A (en) 1978-06-02

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